US5639401A - Process for the catalytic partial oxidation of hydrocarbons - Google Patents
Process for the catalytic partial oxidation of hydrocarbons Download PDFInfo
- Publication number
- US5639401A US5639401A US08/557,782 US55778295A US5639401A US 5639401 A US5639401 A US 5639401A US 55778295 A US55778295 A US 55778295A US 5639401 A US5639401 A US 5639401A
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- United States
- Prior art keywords
- catalyst
- process according
- feed
- oxygen
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- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 81
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 37
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 34
- 230000003647 oxidation Effects 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 104
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000007789 gas Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 230000035939 shock Effects 0.000 claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 48
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 17
- 229910052703 rhodium Inorganic materials 0.000 claims description 16
- 239000010948 rhodium Substances 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 12
- 229910052741 iridium Inorganic materials 0.000 claims description 11
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 230000000737 periodic effect Effects 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011800 void material Substances 0.000 claims description 2
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000002474 experimental method Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000717 retained effect Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000012876 carrier material Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052762 osmium Inorganic materials 0.000 description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910018404 Al2 O3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000004616 Pyrometry Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ZMSUCOPYHBBQBU-UHFFFAOYSA-N [Rh].[Rh].[Ir] Chemical compound [Rh].[Rh].[Ir] ZMSUCOPYHBBQBU-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- IRICKFRKKGHYBF-UHFFFAOYSA-N europium iridium Chemical compound [Eu].[Ir].[Ir] IRICKFRKKGHYBF-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 description 1
- -1 plates Substances 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/386—Catalytic partial combustion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a process for the catalytic partial oxidation of hydrocarbons, in particular to a process for the preparation of a mixture of carbon monoxide and hydrogen from methane, natural gas, associated gas or other sources of light hydrocarbons.
- the partial oxidation of hydrocarbons for example methane or natural gas, in the presence of a catalyst is an attractive process for the preparation of mixtures of carbon monoxide and hydrogen, known in the art as synthesis gas.
- the partial oxidation of a hydrocarbon is a highly exothermic reaction and, in the case in which methane is the hydrocarbon, proceeds by the reaction:
- A. T Ashcroft et al. disclose the partial oxidation of methane to synthesis gas in the presence of a range of ruthenium-containing catalysts.
- the objective of the experiments was to establish that the partial oxidation process could be carried out under mild conditions and at low temperatures. To this end, the experiments were conducted with a low gas hourly space velocity of 40,000/hr, a pressure of 1 atmosphere and a temperature of about 775° C.
- the catalyst employed comprised small amounts of a solid, powdered catalyst.
- U.S. Pat. No. 5,149,464 is directed to a method for selectively oxygenating methane to carbon monoxide and hydrogen by bringing the reactant gas mixture at a temperature of about 650° C. to 900° C. into contact with a solid catalyst which is generally described as being either:
- M is at least one element selected from Mg, B, Al, Ln, Ga, Si, Ti, Zr and Hf;
- Ln is at least one member of lanthanum and the lanthanide series of elements;
- M' is a d-block transition metal, and each of the ratios x/y and y/z and (x+y)/z is independently from 0.1 to 8; or
- the d-block transition metals are said in U.S. Pat. No. 5,149,464 to be selected from those having atomic number 21 to 29, 40 to 47 and 72 to 79, the metals scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold. It is stated in U.S. Pat. No. 5,149,464 that the preferred metals are those in Group VIII of the Periodic Table of the Elements, that is iron, osmium, cobalt, rhenium, iridium, palladium platinum, nickel and ruthenium.
- WO 92/11199 specifically discloses experiments in which catalysts comprising iridium, palladium, ruthenium, rhodium, nickel and platinum supported on alumina were applied. All the experiments were conducted under mild process conditions, with typical conditions being a pressure of 1 atmosphere, a temperature of 1050K (777° C.) and a gas hourly space velocity of about 20,000/hr.
- European Patent Application Publication No. 303,438 discloses a process for the catalytic partial oxidation of a hydrocarbonaceous feedstock in which a gaseous mixture of the hydrocarbonaceous feedstock, oxygen or an oxygen-containing gas and, optionally, steam, is introduced into a catalytic partial oxidation zone to contact a catalyst retained therein.
- the catalyst employed in the process may comprise a wide range of catalytically active components, for example palladium, platinum, rhodium, iridium, osmium, ruthenium, nickel, chromium, cobalt, cerium, lanthanum and mixtures thereof.
- refractory oxides such as cordierite, mullite, mullite aluminium titanate, zirconia spinels and alumina.
- the catalyst may be of a variety of forms, for example sheets of corrugated metal packed to form elongate channels therethrough or wire mesh.
- preference is given in EPA 303,438 to the use of catalysts in the form of extruded honeycomb monoliths. These monoliths comprise a large number of parallel channels extending through the structure in the direction of flow of the feed and product gasses.
- EPB 262,947 discloses a process for generating hydrogen by the partial oxidation of a hydrocarbon in which a mixture of the hydrocarbon and oxygen is injected into a mass of a catalyst.
- the catalyst disclosed in EPB 262,947 comprises platinum and chromium oxide supported on a refractory solid.
- the support structures described in EPB 262,947 are monolithic honeycomb supports, of the type used in purifying the exhausts from motor vehicles or from chemical plants, and particulate supports, preferably comprising particles having a maximum dimension of from 1 to 4 mm, for example 1.5 mm.
- the foam monoliths were of alpha-alumina and described as having an open cellular, sponge-like structure.
- the samples employed had a nominal porosity of 30 to 50 pores per inch (ppi).
- the extruded monoliths were cordierite extruded monoliths, having 400 square cells/in 2 and consisted of straight parallel channels giving laminar flows of gases through the channels under the conditions of gas flowrate studied.
- European Patent Application Publication No. 576,096 discloses a process for the catalytic partial oxidation of a hydrocarbon feedstock in which a feed comprising a hydrocarbon feedstock, an oxygen-containing gas and, optionally, steam at an oxygen-to-carbon molar ratio in the range of from 0.45 to 0.75 is contacted with a catalyst in a reaction zone under adiabatic conditions.
- the catalyst comprises a metal from Group VIII of the Periodic Table of the Elements supported on a carrier and is retained in the reaction zone in a fixed arrangement having a high tortuosity.
- a wide range of carrier materials and structures are disclosed in EPA 576,096, including particles of carrier material, metal gauzes and ceramic foams. Suitable materials for use as carrier materials are said to include the refractory oxides such as silica, alumina, titania, zirconia and mixtures thereof. Alumina is stated as being an especially preferred carrier material.
- European Patent Application Publication No. 548,679 discloses a process for the preparation of carbon monoxide and hydrogen by the catalytic partial oxidation of methane in the presence of a catalyst prepared by depositing, as an active component, rhodium and/or ruthenium on a carrier comprising zirconia or stabilized zirconia.
- the catalyst is described in EPA 548,679 as being of any suitable form, such as finely divided powder, beads, pellets, plates, membranes or monoliths.
- the catalytic partial oxidation process is described in EPA 548,679 as being conducted at a temperature of from 350° to 1200° C., preferably from 450° to 900° C.
- Typical operating gas space velocities are described in EPA 548,679 as being in the range of from 1,000 to 40,000 h -1 , preferably from 2,000 to 20,000 h -1 .
- the specific examples of EPA 548,679 describe experiments conducted at atmospheric pressure at temperatures of from 300° to 750° C. and space velocities of 16,000 and 43,000 h -1 . In all the experiments described in EPA 548,679, the catalyst was retained in the form of a fixed bed of particles.
- the specification of European Patent Application No. 93203331.9 contains a description of a process for the catalytic partial oxidation of a hydrocarbon feedstock in which the hydrocarbon is mixed with an oxygen-containing gas and contacted with a catalyst.
- the catalyst is retained in a fixed arrangement having a high tortuosity of at least 1.1 and at least 750 pores per square centimeter.
- the catalyst preferably comprises a catalytically active metal supported on a carrier.
- Suitable carrier materials are described as including the refractory oxides, such as silica, alumina, titania, zirconia and mixtures thereof.
- a catalyst comprising a zirconia ceramic foam as carrier is specifically exemplified.
- An attractive catalytic partial oxidation process for application on a commercial scale would operate at elevated pressures, typically in excess of 10 bar, for example at around 30 bar, and at high gas hourly space velocities, typically of the order of 500,000 to 1,000,000 h -1 . Due to the thermodynamic behavior of the partial oxidation reaction, in order to obtain a high yield of carbon monoxide and hydrogen at elevated pressures, it is necessary to operate the reaction at elevated temperatures. Temperatures on the order of 1000° C. or higher are necessary for obtaining the yields demanded of a commercial process.
- Catalysts for use in such a process comprise one or more catalytically active components supported on a refractory oxide carrier, the carrier being in the form of a monolith.
- the partial oxidation reactions are very exothermic, with typical reaction conditions in excess of 1000° C. being required for successful commercial scale operation.
- major problems can arise in the operation of the partial oxidation process when using a catalyst in the form of a monolith.
- the refractory monolithic catalyst structures are very susceptible to thermal shock under the conditions of very high temperature prevailing in the catalytic partial oxidation process.
- Thermal shocks arise when the catalyst is subjected to a rapid change in temperature, giving rise to substantial temperature gradients across the catalyst structure.
- Thermal shocks may arise during a shut-down of a commercial reactor in the case of an emergency, in which case it will be necessary to rapidly cool the reactor and its contents. Thermal shocks may also be encountered by the catalyst during start-up procedures and during normal process operation when fluctuations in the feed rate and composition occur.
- zirconia-based monolith structures offer a significantly greater resistance to thermal shocks under the operating conditions of the catalytic partial oxidation process than monoliths prepared from other materials.
- the present invention provides a process for the catalytic partial oxidation of a hydrocarbon feedstock, which process comprises contacting a feed comprising a hydrocarbon feedstock and an oxygen-containing gas with a catalyst at elevated temperature under conditions such the catalyst will be susceptible to a thermal shock, the catalyst being in the form of a porous monolithic structure and comprising a catalytically active metal supported on a zirconia-based carrier.
- the process provided by the present invention is particularly advantageous in that the specific catalyst employed has been found to be particularly robust under the extreme conditions prevailing in the presence of the catalytic partial oxidation reactions.
- the process has been found to be robust in circumstances in which the catalyst is subjected to thermal shocks.
- thermal shock is a reference to conditions under which the catalyst experiences rapid changes in temperature over a wide temperature range.
- thermal shock is a reference to conditions under which the temperature experienced by the catalyst will change at a rate of at least 1° C.
- the process of this invention may be applied under conditions such that the thermal shock is at least 10° C. per second over a range of 100° C. Conditions may be applied giving rise to greater thermal shocks, for example at least 50° C. per second over a range of 500° C. The process may be operated with conditions of still greater thermal shock, for example at least 100° C. per second over a range of 500° C., being experienced by the catalyst.
- the process of the present invention may be used to prepare a mixture of carbon monoxide and hydrogen from any hydrocarbon or hydrocarbon feedstock.
- the hydrocarbon is in the gaseous phase when contacting the catalyst.
- the process is particularly suitable for the partial oxidation of methane, natural gas, associated gas or other sources of light hydrocarbons.
- the term "light hydrocarbons" is a reference to hydrocarbons having from 1 to 5 carbon atoms.
- the process may be advantageously applied in the conversion of gas from naturally occurring reserves of methane which contain substantial amounts of carbon dioxide.
- the feed preferably comprises methane in an amount of at least 50% by volume, more preferably at least 70% by volume, especially at least 80% by volume.
- the hydrocarbon feedstock is contacted with the catalyst as a mixture with an oxygen-containing gas.
- Air is suitable for use as the oxygen-containing gas.
- substantially pure oxygen as the oxygen-containing gas may be preferred. In this way, the need for handling a large volume of inert gas, for example nitrogen when using air as the oxygen-containing gas, is avoided.
- the feed may optionally comprise steam.
- the hydrocarbon feedstock and the oxygen-containing gas are preferably present in the feed in such amounts as to give an oxygen-to-carbon ratio in the range of from 0.3 to 0.8, more preferably, in the range of from 0.45 to 0.75.
- References herein to the oxygen-to-carbon ratio refer to the ratio of oxygen in the from of molecules (O 2 ) to carbon atoms present in the hydrocarbon feedstock.
- the oxygen-to-carbon ratio is in the range of from 0.45 to 0.65, with oxygen-to-carbon ratios in the region of the stoichiometric ratio of 0.5, that is ratios in the range of from 0.45 to 0.65, being especially preferred.
- the steam-to-carbon ratio is preferably in the range of from above 0.0 to 3.0, more preferably from 0.0 to 2.0.
- the hydrocarbon feedstock, the oxygen-containing gas and steam, if present, are preferably well mixed prior to being contacted with the catalyst.
- the process of the present invention may be operated at any suitable pressure.
- elevated pressures that is pressures significantly above atmospheric pressure are most suitably applied.
- the process may be operated at pressures in the range of up to 150 bara.
- the process is operated at pressures in the range of from 2 to 125 bara, especially from 5 to 100 bara.
- the process may be operated at any suitable temperature. Under the preferred conditions of high pressure prevailing in processes operated on a commercial scale, the feed is preferably contacted with the catalyst at high temperatures. This is necessary if high levels of conversion are to be achieved at the preferred elevated pressures. Accordingly, the feed mixture is preferably contacted with the catalyst at a temperature in excess of 950° C., more preferably at a temperature in the range of from 950° to 1400° C., especially from 1000° to 1300° C. The feed mixture is preferably preheated prior to contacting the catalyst.
- gas space velocities for the process are in the range of from 20,000 to 100,000,000 Nl/kg/hr, more preferably in the range of from 5,000 to 50,000,000 Nl/kg/hr. Space velocities in the range of from 500,000 to 30,000,000 Nl/kg/hr are particularly suitable for use in the process.
- the catalyst employed in the process of the present invention comprises a catalytically active metal supported on a monolithic zirconia-based structure.
- Catalytically active metals for inclusion in the catalyst are selected from Group VIII of the Periodic Table of the Elements. References herein to the Periodic Table are to the CAS version, as published in the CRC Handbook of Chemistry and Physics, 68th Edition.
- Preferred catalysts for use in the process of the present invention comprise a metal selected from ruthenium, rhodium, palladium, osmium, iridium and platinum. Catalysts comprising ruthenium, rhodium or iridium as the catalytically active metal are particularly preferred. Iridium is a most suitable catalytically active metal.
- the catalyst comprises the catalytically active metal supported on a zirconia-based carrier. Any suitable zirconia-based material may be employed. Suitable zirconia materials are available commercially.
- the carrier preferably comprises at least 90% by weight zirconia. Stabilized zirconia or substantially pure zirconia are particularly preferred zirconia-based materials.
- the carrier is in the form of a porous monolithic structure.
- the monolithic structure may comprise one or a plurality of individual monolithic portions of carrier.
- the porous monolithic structure may have any suitable form.
- One form of monolithic structure is that of an extruded honeycomb, suitable materials of which are known in the art and available commercially.
- the extruded honeycomb material are characterized by having a plurality of straight, elongate, parallel channels extending through the structure.
- preferred monolithic structures are those having a high tortuosity.
- the term "tortuosity" is a common term in the art which, as used herein, is defined as the ratio of the length of the path followed by a gas flowing through the structure to the length of the shortest possible straight line path through the structure.
- the monolithic structure employed in the process of the present invention preferably has high tortuosity, that is a tortuosity of greater than 1.1.
- the monolithic structure preferably has a tortuosity in the range of from 1.1 to about 10.0, more preferably in the range of from 1.1 to about 5.0.
- a most suitable range of tortuosity for the monolithic structure is from 1.3 to 4.0.
- the monolithic structure employed in the process of this invention is porous.
- the monolithic structure is preferably of high porosity. References herein to porous are to a material having pores with a diameter of the order of 0.1 mm. These pores are to distinguished from the micropores which may be present in the carrier material.
- the monolithic structure preferably contains at least 500 pores per square centimeter, more preferably at least 750 pores per square centimeter.
- Preferred monolithic structures are those having from 1,000 to 15,000 pores per square centimeter, more preferably from 1,250 to 10,000 pores per square centimeter.
- the monolithic structure preferably has a void fraction in the range of from 0.4 to 0.9, more preferably from 0.6 to 0.9.
- a most suitable and especially preferred monolithic structure for the catalyst carrier employed in the process of the present invention is a foam.
- Suitable zirconia foams for use in the process of this invention are available commercially.
- the catalyst employed in the process of the present invention may be prepared by processes known in the art.
- a most suitable process is the impregnation of the zirconia-based material with a compound of the catalytically active metal.
- the feed is preferably contacted with the catalyst under adiabatic conditions.
- adiabatic is a reference to reaction conditions under which substantially all heat loss and radiation from the reaction zone is prevented, with the exception of heat leaving in the gaseous effluent stream of the reactor.
- the present invention relates to carbon monoxide or hydrogen whenever prepared by a process as hereinbefore described.
- the carbon monoxide and hydrogen produced by the process of this invention may be used in any process employing either one or both of these compounds.
- the mixture of carbon monoxide and hydrogen prepared by the process is particularly suitable for use in the synthesis of hydrocarbons, for example by means of the Fischer-Tropsch process, or for the synthesis of oxygenates, for example methanol.
- Processes for the conversion of carbon monoxide and hydrogen into such products are well known in the art.
- the carbon monoxide and hydrogen product may be used in the manufacture of hydrogen by the water gas shift reaction.
- Other applications for the products include hydroformylation and carbonylation processes.
- zirconia foam (ZrO 2 , 990 pores per square centimeter) was impregnated with rhodium using conventional foam impregnation techniques to give a final rhodium loading of 5% by weight.
- the impregnated zirconia foam was loaded into a steel reactor.
- the catalyst structure had a tortuosity of between 1.5 and 2.5. Natural gas and oxygen were thoroughly mixed and the resulting mixture used as feed and introduced into the reactor to contact the catalyst.
- the feed had an oxygen-to-carbon ratio of 0.54.
- the feed was supplied at a gas hourly space velocity (GHSV) of 750,000 Nl/kg/hr (normal liters of gas per kilogram of catalyst per hour) and at a pressure of 1.0 bara.
- GHSV gas hourly space velocity
- the operating temperature of the catalyst was measured by optical pyrometry.
- the composition of the gas leaving the reactor was measured by gas chromatography.
- the conversion and selectivity of the process to carbon monoxide and hydrogen was determined.
- the operating conditions and the results of the experiment are summarized in the Table hereinbelow.
- the feed was preheated to a temperature of 250° C. Initially, however, no reaction was observed. A small region of the catalyst was ignited using heat generated by the combustion of a mixture of propane and oxygen. This resulted in a rapid ignition of the entire catalyst structure, observable as a glow extending rapidly across the catalyst structure from the ignition point in a few seconds. In this time, the entire catalyst was rapidly heated from the initial temperature of 250° C. to the final operating temperature of 1240° C. The catalyst was thus subjected to a thermal shock of greater than 60° C. per second over a temperature range of 990° C. A description of the catalyst at the end of the experiment is given in the Table hereinbelow.
- a commercially available zirconia foam (ZrO 2 , 990 pores per square centimeter) was impregnated with iridium using conventional impregnation techniques to give a final iridium loading of 5% by weight.
- Example 1 The general experimental procedure described in Example 1 above was followed to test the iridium/zirconia catalyst.
- the operating conditions and results of the experiment are set out in the Table hereinbelow.
- zirconia foam (ZrO 2 , 990 pores per square centimeter) was impregnated with rhodium using conventional impregnation techniques to give a final rhodium loading of 5% by weight.
- Example 1 The general experimental procedure described in Example 1 above was followed to test the rhodium/zirconia catalyst.
- the operating conditions and results of the experiment are set out in the Table hereinbelow.
- a commercially available alumina foam (Al 2 O 3 ) was impregnated with rhodium using conventional impregnation techniques to give a final rhodium loading of 5% by weight.
- Example 1 The general experimental procedure described in Example 1 above was followed to test the rhodium/alumina catalyst.
- the operating conditions and results of the experiment are set out in the Table hereinbelow.
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Abstract
Description
2CH.sub.4 +O.sub.2 →2CO+4H.sub.2
TABLE __________________________________________________________________________ Example No. 1 2 3 4 Active Metal Rhodium Iridium Rhodium Rhodium Carrier Zirconia Zirconia Zirconia Alumina foam foam foam foam Operating Conditions Feed Temperature 250 250 180 180 (°C.) Operating 1240 1265 1290 1070 Temperature (°C.) Pressure (bara) 1.0 1.0 1.0 1.0 GHSV 750 750 750 900 (1000 Nl/kg/hr) oxygen/carbon ratio 0.54 0.55 0.55 0.55 CH.sub.4 conversion (%) 98.8 99.2 97.7 87 CO selectivity (%).sup.1 94.2 94.2 95.2 93 H.sub.2 selectivity (%).sup.2 95.5 94.9 93.8 83 runtime (hours) 3 3 2 1 Catalyst thermal >60° C./sec >60° C./sec >60° C./sec >60° C./sec shock** over 990° C. over 1015° C. over 1110° C. over 890° C. Description of Undamaged Undamaged Undamaged Shattered catalyst at end of into many runtime fragments __________________________________________________________________________ .sup.1 selectivity to CO based on CH.sub.4 conversion .sup.2 selectivity to H.sub.2 based on CH.sub.4 conversion *Thermal shock as experienced by catalyst during start up
Claims (14)
Priority Applications (15)
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DZ950096A DZ1918A1 (en) | 1994-08-02 | 1995-07-26 | Process for partial catalytic oxidation of hydrocarbons. |
ZA956360A ZA956360B (en) | 1994-08-02 | 1995-07-31 | Process for the catalytic partial oxidation of hydrocarbons |
JP1996506215A JP4020428B6 (en) | 1994-08-02 | 1995-08-01 | Hydrocarbon catalytic partial oxidation process |
CN95194439A CN1056585C (en) | 1994-08-02 | 1995-08-01 | Process for catalystic partial oxidation of hydrocarbons |
NZ291436A NZ291436A (en) | 1994-08-02 | 1995-08-01 | Catalytic partial oxidation of a hydrocarbon feedstock to produce hydrogen and cabon dioxide using a porous monolihic zirconia based structure |
DE69517033T DE69517033T2 (en) | 1994-08-02 | 1995-08-01 | METHOD FOR THE CATALYTIC PARTIAL OXIDATION OF HYDROCARBONS |
RU97103363/12A RU2154015C2 (en) | 1994-08-02 | 1995-08-01 | Method of partial catalytic oxidation of hydrocarbons |
AU32566/95A AU693245B2 (en) | 1994-08-02 | 1995-08-01 | Process for the catalytic partial oxidation of hydrocarbons |
BR9508457A BR9508457A (en) | 1994-08-02 | 1995-08-01 | Process for the partial catalytic oxidation of hydrocarbons |
EP95929071A EP0773906B1 (en) | 1994-08-02 | 1995-08-01 | Process for the catalytic partial oxidation of hydrocarbons |
ES95929071T ES2149370T3 (en) | 1994-08-02 | 1995-08-01 | PROCEDURE FOR PARTIAL CATALYTIC OXIDATION OF HYDROCARBONS. |
PCT/EP1995/003090 WO1996004200A1 (en) | 1994-08-02 | 1995-08-01 | Process for the catalytic partial oxidation of hydrocarbons |
CA002196433A CA2196433C (en) | 1994-08-02 | 1995-08-01 | Process for the catalytic partial oxidation of hydrocarbons |
US08/557,782 US5639401A (en) | 1994-08-02 | 1995-11-13 | Process for the catalytic partial oxidation of hydrocarbons |
NO970399A NO970399D0 (en) | 1994-08-02 | 1997-01-30 | Process for Catalytic Partial Oxidation of Hydrocarbons |
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US08/557,782 US5639401A (en) | 1994-08-02 | 1995-11-13 | Process for the catalytic partial oxidation of hydrocarbons |
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BR (1) | BR9508457A (en) |
CA (1) | CA2196433C (en) |
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DZ (1) | DZ1918A1 (en) |
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Also Published As
Publication number | Publication date |
---|---|
RU2154015C2 (en) | 2000-08-10 |
JPH10503462A (en) | 1998-03-31 |
EP0773906B1 (en) | 2000-05-17 |
JP4020428B2 (en) | 2007-12-12 |
ZA956360B (en) | 1996-03-11 |
CA2196433C (en) | 2007-09-11 |
BR9508457A (en) | 1997-11-04 |
DE69517033T2 (en) | 2000-11-16 |
CA2196433A1 (en) | 1996-02-15 |
EP0773906A1 (en) | 1997-05-21 |
NO970399L (en) | 1997-01-30 |
NO970399D0 (en) | 1997-01-30 |
CN1154684A (en) | 1997-07-16 |
AU3256695A (en) | 1996-03-04 |
WO1996004200A1 (en) | 1996-02-15 |
ES2149370T3 (en) | 2000-11-01 |
DE69517033D1 (en) | 2000-06-21 |
CN1056585C (en) | 2000-09-20 |
NZ291436A (en) | 1998-08-26 |
DZ1918A1 (en) | 2002-02-17 |
AU693245B2 (en) | 1998-06-25 |
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